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Method for synthesizing 2-substituted-1,4-naphthoquinone compound

A compound, naphthoquinone technology, applied in the field of organic compound synthesis, can solve the problems of polluted transition metal catalyst, unrecyclable, single source of raw materials, etc., and achieves low cost and low toxicity of oxidant, energy saving, and substrate universality. Good results

Active Publication Date: 2017-01-11
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the existing method for synthesizing aryl naphthoquinones has the following shortcomings: (1) generally use some transition metal catalysts that are relatively expensive and polluted, and cannot be recycled, (see Kamal M Dawood. et al. Tetrahedron, 2007, 63(39): 9642-9645; Yuta Fujiwara. et al. J.Am.Chem.Soc., 2011, 133(10): 3292-3295;
(2) low reaction selectivity, poor universality and low yield (see Pravin Patil et al. J.Org.Chem., 2014,79, 2331-2336; Mar1'a Teresa Molina et al. 2009, 21(11)) etc.
(3) Long reaction time, complex post-processing, and serious pollution (see Yuta Fujiwara et al. J.Am.Chem.Soc., 2011, 133(10): 3292-3295), etc.
(4) The source of raw materials is single, which has great limitations on the synthesis of derivatives

Method used

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  • Method for synthesizing 2-substituted-1,4-naphthoquinone compound
  • Method for synthesizing 2-substituted-1,4-naphthoquinone compound
  • Method for synthesizing 2-substituted-1,4-naphthoquinone compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033]

[0034] Add 44.0mg (0.2mmol) o-phenylethynyl acetophenone, 1.28mg (0.02mmol) Cu powder, 141.7mg (0.4mmol) Selectfluor, 19.6mg (0.2mmol) potassium acetate into a 10mL round bottom flask, and then add 2mL of acetonitrile / water (V:V=1:1) was used as solvent. Then, magnetically stir at 70° C. for 12 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) As an eluent, collect the eluent containing the product, and evaporate the solvent from the eluent to obtain the pure product 2-phenyl-1,4-naphthoquinone. The material was a yellow solid, 83% yield.

[0035] Characterization data: 1 H NMR (CDCl 3 ,500MHz): δ8.20-8.18(m, 1H), 8.13-8.12(m, 1H), 7.60-7.58(m, 2H), 7.50-7.48(m, 3H), 7.09(s, 1H);13 C NMR (CDCl 3 , 125MHz): δ185.0, 184.3, 148.1, 135.2, 133.8, 133.8, 133.4, 132.5, 132.1, 130.0, 129.4, 128.4, 127.0, 125.9.

Embodiment 2

[0037]

[0038] Add 50.9 mg (0.2 mmol) 2-o-chlorophenylethynylacetophenone, 3.98 mg (0.04 mmol) CuCl, 70.58 mg (0.2 mmol) Selectfluor, 27.6 mg (0.2 mmol) potassium carbonate to a 10 mL round bottom flask , and then added 2 mL of acetonitrile / water (V:V=2:1) ​​as a solvent. Then, magnetic stirring was performed at 70° C. for 24 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) As an eluent, collect the eluent containing the product, and evaporate the solvent from the eluent to obtain the pure product 2-(2-chlorophenyl)-1,4-naphthoquinone. The material was a yellow solid in 85% yield.

[0039] Characterization data: 1 H NMR (CDCl 3 ,500MHz): δ=8.20-8.16(m, 2H), 7.82-7.81(m, 2H), 7.52(dd, J1=7.5Hz, J2=1Hz, 1H), 7.44-7.38(m, 2H), 7.31 (dd, J1=7.5Hz, J2=2Hz, 1H), 7.02(s, 1H); 13 C NMR (CDCl 3 , 125MHz): δ184.9, 183.1, 148.2, 137.4, 134.0, 133.9, 133.2,...

Embodiment 3

[0041]

[0042] Add 46.8 mg (0.2 mmol) 2-o-methylphenylethynylacetophenone, 1.28 mg (0.02 mmol) Cu powder, 141.7 mg (0.4 mmol) Selectfluor, 4.2 mg (0.1 mmol) potassium formate to a 10 mL round bottom In the flask, 2 mL of acetonitrile / water (V:V=5:1) was added as a solvent. Then, magnetically stir at 70° C. for 12 h. Then, 1g of column chromatography silica gel (100-200 mesh) was added to the reaction solution, and the solvent was removed by distillation under reduced pressure. : 1) As an eluent, collect the eluent containing the product, and evaporate the solvent from the eluent to obtain the pure product 2-(2-methylphenyl)-1,4-naphthoquinone. The material was a yellow solid, 63% yield.

[0043] Characterization data: 1 H NMR (CDCl 3 ,500MHz): δ8.19-8.15(m, 2H), 7.81-7.79(m, 2H), 7.39-7.36(m, 1H), 7.32-7.27(m, 2H), 7.20(dd, J1=7.5Hz , J2=1Hz, 1H), 6.95(s, 1H), 2.25(s, 3H); 13 C NMR (CDCl 3 , 125MHz): δ185.2, 184.0, 150.7, 136.9, 136.2, 133.9, 133.9, 132.3, 132.2, 13...

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Abstract

The invention discloses a method for synthesizing a 2-substituted-1,4-naphthoquinone compound. The method comprises the following steps: by taking a 2-alkynyl acetophenone compound of a formula I as shown in the specification as a raw material, in the presence of a copper catalyst, by taking Selectfluor as an oxidant, adding an alkali substance, performing a stirring reaction for 10-24 hours at 70 DEG C in a mixed solvent of acetonitrile and water, and after the reaction is completed, and performing aftertreatment on reaction liquid, thereby obtaining the 2-substituted-1,4-naphthoquinone compound of a formula II as shown in the specification. By adopting the method disclosed by the invention, the raw materials are variable, a great amount of derivatives can be generated, the catalyst is cheap and easy to obtain, the cost can be greatly lowered, and no pollution can be caused; oxygen sources used in the method are water and Selectfluor; the reaction condition is gentle, and energy consumption can be reduced; in addition, the method has the characteristics of being high in yield, good in substrate universality, simple and convenient in aftertreatment operation, and the like.

Description

[0001] (1) Technical field [0002] The invention belongs to the technical field of organic compound synthesis, and in particular relates to a synthesis method of 2-substituted-1,4-naphthoquinone compounds. [0003] (2) Background technology [0004] Naphthoquinones are a class of small molecular compounds that widely exist in nature. Due to their diverse biological activities, they are widely used in heterogeneous fields such as medicine, pesticides and dyes. Naphthoquinone is an important raw material in fine chemicals. It is used as an intermediate for dyes, medicines, spices, pesticides, plasticizers, etc. It is a polymerization regulator for synthetic rubber and resin, and an important substance for the synthesis of new paper cooking aids. At the same time, naphthoquinone compounds have good anti-corrosion, bactericidal and anti-ultraviolet functions, and are used in dye intermediates. Not only that, many naphthoquinone compounds show unique anti-tumor effects, such as sh...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C46/02C07C50/10C07C50/24C07C50/32
CPCC07C46/02C07C50/10C07C50/24C07C50/32
Inventor 刘运奎汪衡张剑
Owner ZHEJIANG UNIV OF TECH
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